Pentavalent phosphorus esters



Chemical Company, St. Louis, Mo., a corporation of Delaware No Drawing. Filed July 21, 1959, Ser. No. 828,464

Y is Claims. or. 260-461) The present invention relates to organic compounds of phosphorus and more particularly provides a new and valuable class of compounds having a plurality of pentavalent phosphorus ester radicals, the method of preparing the same, and leaded hydrocarbon fuels containing the presently provided compounds as preignition agents.

An object of the present invention is to provide polyphosphorus esters wherein phosphorus is present only in the pentavalent state. Another object of the invention is to provide polyphosphorus esters of good hydrolytic stability. Still another object of the invention is to provide a means of improving the hydrolytic stability of certain compounds containing one or more pentavalent phosphorus ester radicals and a single trivalent phosphorus ited States Patent 3,fil4,%6 Patented Dec. 25, 1961 The compound (I) has the general formula 2 o ROPO CHI E R' wherein R, R and Z are as herein defined. I have now found that compounds of this general formula isomerize ester radical by changing the latter into the pentavalent phosphorus ester radical. A further object of the inven tion is to provide stable, chlorine-containing, organic phosphorus compounds for use as preignition and spark plug antifouling agents for leaded gasoline.

These and other objects hereinafter disclosed are provided by the invention wherein there are prepared compounds having a plurality of pentavalent phosphorus ester radicals and being selected from the class consisting of phosphorus diesters of the formula 0 Z H I ll R-POCHPR I t R and polyesters of the formula 0 0 Z ailotailotaia wherein R is selected from the class consisting of haloalkyl, haloalkenyl, alkoxyhaloalkyl and aryloxyhaloalkyl radicals of from 1 to 12 carbon atoms wherein halo denotes chlorine or bromine, R' is selected from the class consisting of --OR, -O-hydrocarby1 and hydrocarbyl radicals of from 1 to 12 carbon atoms and aromatic halohydrocarbyl radicals of from 6 to 12 carbon atoms, Z is selected from the class consisting of hydrogen, hydrocarbyl, halohydrocarbyl, cyanohydrocarbyl, carboalkoxyhydrocarbyl, alkoxyhydrocarbyl and alkylthiohydrocarbyl radicals of from 1' to 17 carbon atoms and the thienyl and furyl radicals and n is a number of at least 1.

Compounds of the above formula are prepared by heating the reaction products obtained by mixing together a phosphoroor phosphonohalidite, an aldehyde and a trivalent phosphorus ester.. Temperatures of, say, 135

C. to 225 C., depending upon the nature of said reaction products, are employed. Generally, temperatures'of 165 C, to 210 C. are preferred. As disclosed in my copending application Serial No. 780,262 filed December 15, 1958, mixing together bis(2-chloroethyl) phosphorochloridite, acetaldehyde and tris(2-ch1oroethyl) phosphite in substantially equimolar proportions gives (1) the bis(2-chloroethyl) phosphite of bis(2-chloroethyl). l-hydronyethylphosphonate, thus:

ll (ClCHaCHzOMP O C|H-P (O CHaCHzCl) ri-CHzQlCHzCl OHa upon heating, say, at a temperature of from 225 C. to give esters in which no trivalent phosphorus is present,

In the case of the above compound (I), the isomerization takes place according to the scheme:

w t (C1CH2CH20)2POGHP(O CH2CHzC1)ztfi t CICHzCHzOPOCH-P(OCH2CH2C1)2 'onzonioi The product thus obtained is a diphosphonate, rather than a phosphite-phosphonate.

Also useful for the preparation of compounds having more than one pentavalent phosphorus ester radical and no trivalent phosphorus are compounds obtained from phosphorochloridites having dissimilar alcohol residues; for example, methyl 2-chloroethy1 phosphorochloridite, butyraldehyde and tris(2-chloropropyl) phosphite react in equimolar proportions to give a phosphite-phosphonate which upon heat treatment is converted as follows:

I ll olornorno P0 OHP(O onionolonae- 0115-0 CHrCHzCHs It will be noted that in the isomerization only a halogen-containing alcohol residue of the phosphorohalidite reactant is involved. Hence, products prepared from a phosphorohalidite, an aldehyde and a phosphonite or phosphinite instead of a phosphite likewise give pentavalent phosphorus diesters or polyesters. The equimolar reaction product of, say, bis(2-chloropropyl) phosphorochloridite, propionaldehyde and diethyl phenylphosphonite isomerizes as follows: I

OHaCHz O (CHaCHOlCH O) P-O CHlIO CHzCHa' II II CHaCHClCHaO-P-O CH-P-O OHzCHa OHZQMIJH CH2 CeHs CH3 CH3 The isomerizaticn product obtained from the equimolar reaction'product of a phosphinite such as ethyl di-n-propylphosphinite and the same phosphorochloriditeand the same aldehyde has the structure The compound which is formed from a 1:111 molar mixture of the trivalent phosphorus halogen compound,

the aldehyde and the trivalent phosphorus ester is a phosphite-phosphonate when the ester and the halidite are derived from phosphorous acid, thus:

where R is selected from the class consisting of haloalkyl, haloalkenyl, alkoxyhaloalkyl and a-ryloxyhalo-alkyl radicals of from 1 to 12 carbon atoms, and T is selected from the class consisting of R and alkly radicals of from 1 to 12 carbon atoms. It isomerizes upon heating to When the ester and the halidite are derived from a hydrocarbyl or halohydrocarbylphosphonous acid, the 1:1:1

product is a phosphonitephosphinate, thus:

o ROPX+i H+P-(OR) ROP0-OHi"OR+RX l t t Y t t where Y is a hydrocarbyl or halohydrocarbyl radical. It isomerizes to give the diphosphinate:

When the ester is derived from phosphorous acid and the halidite is derived from a phosphonous acid, the 1:1:1 product is a phosphonite-phosphonate, thus:

It isomerizes to give the phosphinate-phosphonate:

R-i OCH-1| -OR Y Z OR When the ester is derived from a phosphonous acid and the halidite is derived from phosphorous acid, the prod- When the ester is derived from phosphinous acid and the halidite is derived from a phosphorous acid, the product is a phosphite-phosphine oxide:

Similarly, with the same ester and a phosphonohalidite instead of the phosphorohalidite, the product is a phosphonite-phosphine oxide:

It isomerizes to give the phosphinate-phosphine oxide:

I? II Y z Y The 1:1:1 reaction products are thus phosphite-phosphonates, phosphonite phosphinates, phosphonite-phosphonates, phosphite phosphinates, phosphite-phosphine oxides, or phosphonite-phosphine oxides. There is always present one trivalent phosphorus ester group and one pentavalent phosphorus ester group. According to the present invention these 1:1:1 reaction products are isomerized by heating at C.-225 C. to give diphosphonates, diphosphinates, phosphinate-phosphonates, phosphonate-phosphinates, phosphonate-phosphine oxides, and phosphinate-phosphine oxides.

Also isomerized upon heating at, say, 135225 (3., are the polyphosphorus esters disclosed in my copending application, Serial No. 820,618 filed June 16, 1959 which esters are formed when a mole of the trivalent phosphorus halogen compound and a mole of an aldehyde are contacted with less than one mole of the phosphorus ester. The polyphosphorus esters disclosed in said copending application have the formula where R, R and Z are as above defined and n is at least one.

The products provided by the present invention are prepared by heat isomerization of the above. The present compounds, having no trivalent phosphorus, have the formula:

0 0 z 0 alloalgloata R! R! J R! wherein R, R and Z are as herein defined and n has a value of at least one. It will be noted that the above formula is like that of the isomerization products of the compounds obtained from equimolar mixtures of the phosphorus halogen compound, the aldehyde and the phosphorus ester, except for the unit or units i ii -0 CHP wherein R, Rand Z are as herein defined, X is chlorine or bromine, and T is an alkyl or haloalkyl radical of 1 to 12 carbon atoms.

From the above, it is apparent that the presence of repeating uni-ts [was] t f t in a product prepared from the ester R' POR, the phosphorus halide and the aldehyde depends upon whether the quantity of the phosphite present in the initial reaction mixture is less on a molar basis than the quantity of phosphorohalidite and aldehyde. Whenever it is less, the 1:1: 1 reaction product functions as a trivalent phosphorus ester RP(OR) and reacts with the excess of halidite and aldehyde present. As shown schematically above, the product thus formed in turn functions as a trivalent phosphorus ester in the reaction with halidite and aldehyde so that, depending upon the available halidite and aldehyde, there are obtained polyphosphorus compounds of the formula o l l n ROPOCHl -O CHPR where n is at least 1. The value of n increases rapidly owing to the participation of the successively formed intermediate ester products, so that when there is present a large excess of the halidite and the aldehyde, or when these two reactants are constantly replenished, n is a number of, say, from 1 to 100. Generally, the product consists of mixtures of compounds of the above formula in which there are present products wherein the value of It varies.

Although a convenient means of preparing the pres- ,ently used polyphosphorus compounds comprises employing, in an initial reaction mixture, less than an equimolar quantity of trivalent phosphorus ester with respect to the phosphorus halide and aldehyde, the polyphos- .phorus compounds can also be prepared by starting with a previously prepared 1: 1:1 reaction product and adding the phosphorus halide and the carbonyl compound thereto. Thus, from a 1:1:1 mixture of a phosphorus halogen compound such as bis(Z-chloroethyl) phosphorochloridite, an aldehyde such as propionaldehyde and a trivalent phosphorus ester such as triethyl phosphite there is obtained, according to the process of my copending application, Serial No. 780,209, filed December 15, 1958, the bis(Z-chloroethyl) phosphite of diethyl l-hydroxy propylphosphonate:

This compound can then be converted to one having a plurality of pentavalent phosphorus radicals by reacting it with additional quantities of the bis(Z-chloroethyl) phos phorochloridite and of the propionaldehyde to give the phosphite-polyphosphonate where n is a number of at least 1. Or, instead of using the same trivalent phosphorus halide and the same aldehyde which was used for preparing the bis(2-chloroethyl) phosphite of diethyl 1-hydroXy-propylphosphonate, there may be used a different trivalent phosphorus halide, e.g., 2-chloroethyl ethyl phosphonochloridite and a ditferent aldhehyde, e.g.,benzaldhyde. In this case the reaction proceeds as follows: 1

OHzCl It is thus apparent that in the repeating units tlttll t where x is zero when equimolar quantities of the three reactants are employed and is at least one when the proportion of said ester is less than equirnolar with respect to each of the other two reactants. Depending upon the ratio of the three reactants, the average value of x may obviously be a number of between zero and one, i.e., the reaction mixture can consist of the 1:1:1 halidite-aldehyde-ester product in a mixture with products wherein x (M15 is one or more. The trivalent phosphorus ester portion of either said 1:1:l products or of the nolvohosuhorus CHSCH2P OCH POCH compounds isomerizes upon heating at, say 135-225 C., OHQOHCICHZO the general formula for the presently provided pentava- 5 00H: 0

lent phosphorus ester products being: cmcmr o CH--P-O 0 H;

(6 r l 6 OHzClCHCI-Ia O-GQH! T H That obtained from less than an equimolar proportion R Z R x Z 10 of the phosphite reacts as follows:

where x denotes the average number of bracketed units, Cum 0 OGHE O which number may be zero or more. r II 1 I As hereinbefore stated, the reaction products which are CH3CH PTOCH J obtained from equimolar mixtures of the three reactants onionoiom onion; n o-onn and those obtained from one mole of the halidite, one 0 0 11 t") '1 C6H5 0 mole of the aldehyde and less than one mole of the ester CHSCHIJEL i isomerize when heated at 135-225 C. according to the L J l invention to give products wherein the phosphorus is 03101911 HflOHB @0115 present in only the pentavalent form, thus: H

l i I 1 H Also, the reaction product of one mole of 2-ch1oroethy1 ROP--O OHP--OCH-PR phenylphosphonochloridite, one mole of acetaldehyde n 5 and one mole of diethyl n-propylphosphonite is convert- 0 1 Z 0 ed by heating to the disphosphinate: R-i o( 1ri ooH-i R' CH5 0 1'1 L I a n 1 1 CgHs-POH-POCH:CH:-" For example, the product obtained from one mole of bis- 01011101120 91120310111 (2-ch1oropropyl) phosphorochloridite, one mole of form- 0 CH; O

aldehyde and less than one mole of triethyl phosphite 0 i 00H,0

is converted upon heating at 135-225 C. to the polyphosof less eqllimolar quantity Phos' Similar isomerization is evidenced by the product prephonlte or a phosphimte with respect to the halid te and pared from the same reactants in a proportion wherein the aldeilyde glves polyphosphoms compounfis whlch 4 the phosphonite is present in less than equimolar ratio. on heatmg at 135*2250 rearrange to give the with respect to the other two reactants, thus: following from the phosphonite:

OH: (I? "I (iHa HPOOHP OCH-POCH CH It W111 be noted from the following instances, wherem C6 5 L 1 a a a there are shown isomerization of either the 1:1:1 phos- ClOHiCHIO CHQCHlCH phorus halide-aldehyde-ester products or of the poll O I OH: 0 CH: 0 phosphorus esters that only the trivalent phosphorus pori {L L tron of either type of ester 1s involved. 010E CH L C H CH OH OH Compounds obtained from a phosphonochloridite, an I a 5 a a aldehyde and a phosphite undergo similar isomerization. When a phosphinite, Say ethyl ditolylphosphinite is For example, the 1:1:1 reaction product of 2-chloroused as the trivalent ester with the same phosphonochlopropyl ethylphosphonochloridite, benzaldehyde and an n'dite, the heat isomerization products have the formula alkyl diphenyl phosphite gives the phosphinate-phospho- O C nate as follows: 1 CaHs-P OCH-4i H: O (His 0 OCH-P-(GsHtCHI)! o ni The presently provided pentavalent phosphorus dior polyesters are classes of compounds having the following structures wherein R is selected from the class consisting of haloalkyl, haloalkenyl, alkoxyhaloalkyl, and

Riioi l. LR L LBJ,

x 4 X O L Y H Z C O R O vfi O R m ,5 1 m w O n H Z C O R O iP O m O R t S a e l m f O r .m m m m 0 Z Balsam (LR L Z O OLE-l nu by L O 1 CHIL (OY): J,

0 II by 0 LOB LY fi oas LL LY Bil LY L 0 IL L Riimil JR L Z 0 (EH-LOB L on JEEP-OR LX z 0 lO-LJH OR ILL ix The above classes of compounds are all obtainable by jheat isomerization of the reaction product of (1) a halidite of the formula ROPX drocarbyl, halohydrocarbyl, cyanohydrocarbyl, carboalkoxyhydrocarbyl, alkoxyhydrocarbyl, and alkylthiohydrocarbyl radicals of from 1 to 17 carbon atoms and the thienyl and furyl radicals, and (3) a trivalent organic phosphorus ester of the formula TO-P-R in which R is as above defined and T is selected from the'class consisting of alkyl and haloalkyl radicals of from 1 to 12 carbon atoms.

An important class of phosphorus halogen compounds of the above formula are the phosphorohalidites, i.e.,

'carbyl, halohydrocarbyl, carboalkoxyhydrocarbyl, alkyl- I class of aldehydes includes the aliphatic hydrocarbon aldehydes of from 1 to 18 carbon atoms, e.g., formaldehyde,

compounds of the formula (RO) PX. This includes the haloalkyl phosphorohalidites, e.g., bis(2-chloroethyl), bis(2-bromo-3-chloropropyl), bis(3-bromo-2-chloropropyl), bis(2,3-dichloropropyl), bis(2-bromopropyl), bis- (tetrachloropropyl), bis(dichloroamyl), bis(dichlorodo decyl), 2-chloroethyl methyl, allyl Z-bromopropyl, dibromohexyl butenyl or 2-chloropropyl dodecyl phosphorochloridite or phosphorobromidite. Also useful are the haloalkenyl phosphorohalidites, e.g., bis(2-chloro-3- pentenyl) phosphorochloridite obtained by reaction of phosphorus trichloride with 4,5-epoXy-2-pentene.

The alkoxyhaloalkyl or aryloxyhaloalkyl phosphorochloridites obtained by reaction of glycidyl ethers with phosphorus trichloride or phosphorus tribromide are likewise very useful phosphorus-halogen reactants, as will be hereinafter disclosed.

Also useful in the reaction with aldehydes and triorgano phosphites to give the present polyphosphorus compounds are the haloalkyl, haloalkenyl, alkoxyhaloalkyl or aryloxyhaloalkyl esters of hydrocarbylor halohydrocarbylphosphonohalidites, i.e., compounds of the formula wherein R is as above defined and Y denotes a hydrocarbyl or halohydrocarbyl radical of from 1 to 12 carbon atoms.

Presently useful hydrocarbylphosphonohalidites or halohydrophosphonohalidites, include, e.g., 2-chloropropyl phenylphosphonochloridite, 2-bromobutenyl a-naphthylphosphonochloridite, 2-chloroethyl 2-fluoroethylphosphonochloridite, 2-bromoethyl methylphosphonobromidite, trichlorobutyl benzylphosphonochloridite, 2-chloropropyl p-tolylphosphonobromidite, 2-bromoethyl n-butyL .phosphonochloridite, 2-bromo-4-ethoxybutyl p-biphenylphosphonochloridite, 2-chlorethyl phenylphosphonochloridite, 2 bromo 3 hexenyl phenylphosphonochloridite,

.tetrachloropentyl ethylphosphonochloridite, 3 -bromopropyl n-hexylphosphonochloridite, Z-bromopropyl ,8-

.bromo wnaphthylphosphonobromidite, dibromododecyl methylphosphonobromidite, 2 bromoethyl benzylphosphonochloridite, trichlorooctyl cyclohexylphosphonochloand pentavalent phosphorus which upon heating at, say, 1

'l35-225 C. give the presently provided esters which ,contain phosphorus only in the pentavalent form. The

useful aldehydes have the formula ZCHO wherein Z is selected from the class consisting of hydrogen and hydrothiohydrocarbyl, alkoxyhydrocarbyl and cyanohydrocarbyl radicals of from 1 to 12 carbon atoms, and the thienyl and furyl radicals.

Owing to their easy availability, a particularly useful acetaldehyde, acrolein, propionaldehyde, butyraldehyde,

fisobutyraldehyde, crotonaldehyde, valeraldehyde, isovaleraldehyde, hexanal, citronellol, heptanal, tiglic aldehyde, Z-ethylhexanal, octanal, Z-butyloctanal; propargaldehyde, 6-methylheptanal, amylpropiolic aldehyde, de-

canal, undecanal, .2-methylundecanal, lauraldehyde, stearaldehyde, tridecaldehyde, etc. a

The presence of cyano, halogen, alkyl, carboalkoxy, alkoxy and alkylthiosubstituents in the aliphatic aldehyde has no effect on the course of the reaction; hence, there may be employed-such substituted fatty aldehydes dichloropropionaldehyde, chloral, 3-isopropoxypropionaldehyde, 3-(ethylthio)-3-methylbutyraldehyde, 2-methy1-3- fluoropropionaldehyde, dibromostearaldehyde, dichlorolauraldehyde, ethyl ll-formylundecanoate, succinaldehydic acid methyl ester, ethyl 4-formylbutyrate, diethyl formylsuccinate, iodoacetaldehyde, dichloroacetaldehyde, etc.

Presently useful alicyclic carboxaldehydes include cyclohexanecarboxaldehyde, 6 methyl-3-cyclohexenecarboxaldehyde, 2-cyclohexene-l-carboxaldehyde, cyclopentanecarboxaldehyde, 3 isopropyl-1-methylcyclohexane carboxaldehyde, 5 ethoxy 3-cyclopentene-l-carboxaldehyde, 1 bromo 2,2,6 trimethylcyclohexanecarboxaldehyde, 2,2,6-trimethylcyclohexanecarboxaldehyde, 2,2,6- trimethyl 2 cyclohexenecarboxaldehyde, 4 chlorocyclohexanecarboxaldehyde, etc. The heterocyclic aldehydes include furfural and the thiophenecarboxaldehydes.

The presently useful benzenoid aldehydes may be aliphatic-aromatic or purely aromatic aldehydes which may or may not be further substituted, e.g., benzaldehyde, o-, mor p-tolualdehyde, phenylacetaldehyde, dipentylbenzaldehyde, cinnamaldehyde, 1- or Z-napthaldehyde, biphenyl- 4-carboxaldehyde, a-phenylacrolein, hydrocinnamaldehyde, 2,3-dichlorobenzaldehyde, phenylpropargaldehyde, 2-, 3- or 4-butoxybenzaldehyde, mor p-chlorobenzaldehyde, p-(ethoxy)benzaldehyde, 2-ethoxybenzaldehyde, 3,4-dipropoxybenzaldehyde, 4-(n-butylthio)oenzaldehyde, o-, mor p-iodobenzaldehyde, 3,4 or 3,5-dibromobenzaldehyde, 5-tert-butyl-m-tolualdehyde, 5-tert-butyl-3-fluoroo-tolualdehyde, Z-p-cymenecarboxaldehyde, G-methoxy- 2-naphthaldehyde, 2-butoxy-l-naphthaldehyde, 4'-bromo- 4-biphenylcarboxaldehyde, etc.

Triorgano phosphites which are generally useful with the aldehyde and the phosphorus halide to give the presently useful esters are either simple or mixed phosphites. Examples of useful phosphites are trimethyl, triethyl, triallyl, triisopropyl, tri-n-propyl, tri-2-butenyl, triu-butyl, tri-tert-amyl, tri-n-hexyl, tri-n-heptyl, tris(2-ethylhexyl), trioctenyl, tri-n-octyl, trinonyl, tridecyl, triundecyl, tri-tert-dodecyl, tridodecenyl, amyl diethyl, butyl di-n-propyl, n-dodecyl dimethyl, ethyl octyl propyl, tris(2- chloroethyl) tris(3-chloropropyl) tris(2-chloropropyl) tris(3,4-dichlorobutyl), tris(2-chloro-4-pentenyl), tris(2- brornoethyl) tris(3-chloro-2-propenyl) tris(3-iodopropyl), tris(2 fluoroethyl), tris(dichlorododecyl), tris(2- ethoxyethyl), Z-chloroethyl diethyl, tris(2-phenoxypropyl), 3-bron1opropyl bis(2-chloroethyl), diamyl trichlorooctyl, .2-chlo1oethyl 3-chloropropyl 4-chlorobutyl, 2- chloroethyl methyl propyl, tris(2,3-dichloropropyl), tris- (2-bromo-3-chloropropyl) tris(2 chloro-3-methoxypropyl) and tris(2-brorno-4-phenoxybutyl) phosphite.

Instead of the tribasic phosphites there may be employed as the trivalent phosphorus ester component a diester of a hydrocarbyl or halohydrocarbylphosphonite, i.e., a compound of the formula YP(OR) where Y is selected from the class consisting of hydrocarbyl and halohydrocarbyl radicals of from 1 to 12 carbon atoms.

Presently useful phosphonites include, e.g., dimethyl' phenylphosphonite, diethyl 2-propinylphosphonite, ethyl methyl phenylphosphonite, di-n-propyl methylphosphonite, di-n-butyl benzylphosphonite, bis(2-chloroethy1) ptolylphosphonite, bis(2-methoxyethyl) cyclohexylphosphonite, bis(2-ethylhexyl) 2,4-diethylphenylphosphonite, his(2-bromo-3-ethoxypropyl) 2-brorno-ethylphosphonite, diethyl 2-propinylphosphonite, bis(2-butyloctyl) Z-butenylphosphonite, di-n-hexyl p-biphenylphosphonite, diundecyl n-hexylphosphonite, bis(trichloropropyl) 2-methylcyclopentylphosphonite, diethyl 4-n-hexylphenylphosph0- uite, diallyl Z-phenylethylphosphonite, dipentenyl 2-ethylhexylphosphonite, bis(2-chloroethyl) phenylphosphonite, bis(tetrachloropentyl) ethylphosphonite, bis(3-bromopropyl) biphenylylphosphonite, bis(2-chloro-4-phenoxybutyl) methylphosphonite, bis(2-ch1oroethyl) benzylphosphonite, bis(2-bromo-3chloropropyl) phenylphosphoi6 nite, allyl propyl 2,4-dichlorophenylphosphonite, bis-(trichlorooctyl) cyclohexylphosphonite, bis(4-fluorobutyl) 2-cyclohexenylphosphonite, bis(4-chlorobuty1) ethylphosphonite, bis(dichloroheXyl) phenylphosphonite, bis(2- chloropropyl) n-butylphosphonite, din-butyl pentachlorophenylphosphonite, etc.

Presently useful as the ester component are also phosphinites of the formula Y POR wherein Y and R are as herein defined, e.g., the alkyl or alkenyl dihydrocarbylphosphinites such as ethyl, allyl, butyl, n-octyl diethylphosphinite or diphenylphosphinite, benzylcyclohexylphosphinite or diallylphosphinite; the corresponding haloalkyl esters such as 2-chloropropyl di-p-tolyphosphinite or 2-fiuorethyl ethylmethylphosphinite; the ether-substituted esters such as 4-methoxybutyl or 3-phenoxy-2- chloropropyl di-n-butylphosphinite or di-fl-naphthylphosphinite; and the corresponding esters of the halo-substituted phosphinic acids such as the methyl, pently, ethyl, Z-butenyl, 2-chloroethyl, 3-ethoxypropyl, or 4-butoxy-2- bromopentyl esters of bis(2-chloropropyl) phosphinite or of n-butyl(4-chlorophenyl) phosphinite.

The alkyl radical of a trialkyl phosphite, of a dialkyl halohydrocarbylphosphonite, of a dialkyl hydrocarbylphosphonite, or of an alkyl dihydrocarbylphosphinite and halo derivatives thereof may also be one derived from a branched chain alcohol obtained according to the Oxo process by the reaction of carbon monoxide and hydrogen with a higher olefin, e.g., butylene dimer or propylene trimer.

The presently provided pentavalent phosphorus dior polyesters are very conveniently prepared from the trivalent phosphorus-pentavalent phosphorus esters that are prepared by mixing together an aldehyde and the mixture of phosphorohalidite and phosphite which is obtained by reacting phosphorus trichloride or phosphorus tribromide with an oxirane compound. As disclosed in my copending application, Serial No. 780,262, filed December 15, 1958, the reaction of two moles of phosphorus trichloride or phosphorus tribromide with five moles of an olefin oxide, e.g., ethylene oxide, results in the production of an equimolar mixture of a phosphorochloridite and a tribasic phosphite, thus:

OHn- (CEzOlCHzO) P Cl-l-P (O CHzCH Cl);

' phorus trichloride a quantity of alkylene oxide which is less than five moles, but greater than four moles, the reaction product contains less of tribasic phosphite than of phosphorochloridite. For example, using 2 moles of phosphorus trihalide and 4.98 moles of alkylene oxide, the reaction product consists essentially of 0.98 mole of tribasic phosphite and 1.02 moles of phosphorohalidite. Using 2 moles of phosphorus trihalide and 4.95 moles of alkylene oxide, the reaction product consists of about 0.95 mole of phosphite and 1.05 moles of the halidite. As the number of moles of the alkylene oxide per 2 moles or phosphorus trichloride approaches 4, there is an increasingly greater content of phosphorohalidite in the reaction product. The variation of halidite to ester ratio in the reaction product of an alkylene oxide and phosphorus trihalide is shown below.

Moles of alkylene oxide per 2 moles of P01 or PBlg Moles or halidite in product per mole of phosphite The average number of units in the polyphosphorus compounds obtained by reacting the phosphite-halidite mixture with an -aldehyde in a quantity which is at least equimolar with respect to the halidite increases with increasing halidite ratio. When the phosphite to halidite ratio is 0.98:1.02 the reaction product consists of about 96% on a molar basis of the 1:1:1 halidite-aldehyde-ester compound (which has none such unit) and about 4% on a molar basis of a compound having one such unit. :When the phosphite to halidite ratio is 0.95:1.05, the reaction product consists of about 89.5 on a molar basis of a compound having none such units and about 10.5% on a molar'basis of a compound having one such unit. As the halidite content of the phosphorus tn'chloride-alkylene oxide reaction product increases, the number of said units in the product obtained therefrom by reaction with analdehyde increases, as is apparent from the table below:

Average num- Molar ratio of her of repeathalldite to ing units in phosphlte aldehyde product average number of said units in the polyphosphorus coma pound is 100. For practical purposes, and in order to obtain products of value for presently desired'industrial applications, it is preferred to operate in such a manner that the average number of said units is, say, from 1 to 10, and more advantageously from 1 to 4. 4

As will be apparent to those skilled in the art the term average units when applied to repetitive portions of a high molecular weight composition indicates a mixture in which there is present varying numbers of such units. Hence in a composition which is stated to have, say, an, average of repeating units there will be present compounds having less than 10. such units as well as CQUI', pounds having more than 10 uni-ts. g

It is thus apparent that sovlong as there isemployed in the reaction with the aldehyde a mixture of phosphorohalidite and tribasic phosphite which is prepared by reac tion of two moles of phosphorus trihalide with more than four but less than five moles of alkylene oxide, and the quantity of aldehyde used is at least .equimolar with respect to the phosphorohalidite content of the so obtained trihalide alkylene oxide reaction product, there is p r esent in the final reaction product. a substantial quantity of phosphite-polyphosphonate. o

Oxirane compounds suitable for reaction with the phosphorus trichloride or-phosphonustribromide to yield mixt-ures of phosphite and phosphorochloridite that are reacted with an aldehyde to give the compounds which are presently isomerized are, e.g., ethylene oxide and alkyl tane, 2,3-epoxypentane, 2,3-epoxyhexane, 1,2-ep'oxyhex-' ane, 1,2-epoxyheptane, 2,3 epoxy-3-ethylpentane, 1,2 I

epoxy-3,4-dibromobutane,2,3-epoxy-l-bromopentane, 3,4

epoxy-2-chlorohexane, l,2-epoxy-3,3,3-trifiuoropropane, l -bromo-2,3-epoxyheptane; the alkenyl-substituted oxiranes such as 3,4-epoxy-4-methyl-l-pentane and 3,4-epoxyl-butene; aryl-substi-tuted oxiranes such as (epoxyethyD- benzene, (1,2-epoxy-1-methylthyl)benzene, (3-chloro- 1,2-epoxypropyl)benzene; alkoxyalkyland phenoxyalkylsubstituted oxiranes such as the methyl, ethyl, isopropyl,

isoamyl and phenyl ethers of glyoidol, i.e., compounds of the formula CHCHCHzOR where R is methyl, ethyl, isopropyl, amyl ethoxyethyDethylene oxide, etc.

Reaction of two moles of phosphorus trichloride or of phosphorus tribromide with five moles or'with more than four but less than five moles of the presently useful substituted oxiranes gives, by way of example, mixtures of the following phosphites and phosphorohalidites which are advantageously reacted with an aldehyde to give presently useful trivalent phosphorus-pentavalent phosphorus esters:

(I) Tris(2-chloroethyl) phosphite and bis(2-chloroethyl) phosphorochloridite (II) Tn's(2,3 -dichloropropyl) phosphite and bis(2,3-dichloropropyl) phosphorochloridite or phenyl; (2-

(III) Tris(2-chloropropyl) phosphite and bis(2-chloro- (VI) Tris(2,3-dibromopropyl) phosphite and bis(2,3-dibromo-propyl) phosphorobrornidite (VII) Tris(3-bromo-2-chloropropyl) phosphite and bis(3- brorno-Z-chloropropyl) phosphorochloridite (VIII) Tris(2-bromo-3-chloropropyl) phosphite and bis- (XVIII) Tris(2-chloro-2-ethylhexyl) phosphite and his (2-chloro-2-ethylhexyl) phosphorochloridite V (XIX) Tris(3-1nethoxy-2-chloropropyl) phosphite and bis(3-methoxy-2-chloropropyl) phosphorochloridito (XX) Tris(3-phenoxy-2-brornopropyl) phosphite and his- (3-phenoxy-2-bromopropyl) phosphorobromidite (XXI) Tris(2-chloro-4-ethoxybutyl) phosphite and bis- (2-chloro-4 ethoxybutyl) phosphorochloridite (XXII) Tris-(3-bromo-2-chloropropyl) phosphite and his- (3-bromo-2-chloropropyl) phosphorochloridite 19 20 Since reaction of the oxirane compound with the phosesters have the formula phorus trihalide proceeds through opening of the oxirane I! ring, there may be present in the above mixtures minor O H F30 h 1 1k amounts of isomeric phosphite and isomeric phosphorov (haloalk L J C 2 Ma )2 halidite, e.g., While in the reaction-of phosphorus trichlo- 5 I 011a10a1k n Tide and P py Oxide the OXirflIle Ting OPEIIS with where haloalk denotes a 'haloalkyl radical of from 1 to 12 Preferential fhl'mfltion Of p py Phosphite carbon atoms and n is zero or greater. When the aldeahd P Py Phosphhrochloridhe t re m y hyde is a fatty aldehyde, the products obtained from a also be formed small quantities of tris( l-methyl-Z-chloromixture of phosphorohalidite like his(2-chloropropyl)- ethyl) phosphite and bis(l-methyl-Z-chloroethyl) phosphosphorochloridite and a phosphorus ester like tr1s(2- phorochloridite. The isomer content, if any, of the reacchloropropyl) phosphite have the formula:

F ll 1 i (CHsCHClCHzO)9P- (|3HP- O[OHP(0CH;CHC1CH;)2 -ls1k+ all:

ornon'oiorn tion mixture is of no consequence for the present purpose in which alk denotes an alkyl radical of from 1 to 12 carbecause the isomers also react with the carbonyl combon atoms, and n is zero or greater. When the same repound to give phosphite-phosphonates. While the small action product of propylene oxide and phosphorus triquantity of isomeric phosphite-phosphonate present in the chloride is treated with an aromatic aldehyde and the final reaction product may be considered to constitute products have theformula:

ll 1 ll (CHiCHo1CH,o ,P-o ?rrP----ocH-moomorrowrhn aryl 8') J aryl CHzCHClCHa u an impurity, it is not detrimental in practical application in which aryl denotes an aromatic hydrocarbon radical for the isomers are so closely related that they possess f andnis zero or greater. substantially the same utility. Thus, the content of, say, Reaction of the trivalent phosphorus halogen coma small quantity of the bis(1-methyl-2-chloroethyl) phospound, the aldehyde and the trivalent phosphorus ester in phite of bis(1-methyl-2-chloroethyl) (l-hydroxyethyl) the above stated proportions takes place readily by conphosphonate, which may be present along with the bis(2- tacting the three reactants at ordinary or moderately dechloropropyl) phosphite of bis(2-chloropropy l-hycreased or increased temperatures and allowing the result- Y YD phosphonate in the reaction product of aceta ing reaction mixture to stand until formation of the tridehyde and the mixture of phosphite and phosphorochlovalent phosphorus-pentavalent phosphorus ester. Thus, ridite obtained from two moles of phosphorus trichloride the phosphorus halogen compound maybe mixed with th and more than four but less than five moles of p py phosphorus ester in the appropriate ratio or a mixture OXide, gsflefally does not limit the utility of the vlflilefthereof may be prepared from a phosphorus trihalide and However, if d the isomeric p y y be P an oxirane compound as disclosed above, and the alderated y g y known isolaiing Procedures, hyde may be added to the resulting mixture. Or, if dematogfaphy, Crystallization, sired, the aldehyde and the phosphorus ester may first he Reaction of the phosphorus trichloride or phosphorus I mix d and the phosphorus halogen compound added theretribromide with the presently useful oxirane compounds to. Because the reaction may be exothermic, gradual contakes place readily, generally, by simp y i g the pl10 tact of the reactants is usually recommended in order to PhomlS halide with the OXiIflhe Compound in the pp obtain smooth reaction. However, as will be apparent to Priiite Depending on the nature of the individual those skilled' in the art, the exothermal nature of the rereactahts, healing y or y not be r q ir The use action becomes less of a factor as the molecular weight of Of chlialylic amounts of an acidic agent, -8 hydrogen the reactants, and particularly of the phosphorus-containchloride or a compound which produ s hydr e ing reactant is increased. Also, when the aldehyde is ride under the rea ti n'w d ethylene ChlOrO- either a higher alkanecarboxaldehyde or an aralkyl or y 1S advflhlagfious- Usually the faction is 6 alkaryl aldehyde, reaction is generally not so rapid as it is 11110, whereby COOhhg in Order to maintain Smooth with the lower aliphatic aldehydes or with benzaldehyde. action is advantageous It is recommended that in such It is thus recommended that in each initial run, the three exothermic reactions the temperature not be allowed to reactantstbe i d d ll at l temperatures nd th t 1186 above, y, from 41) A11 inert diluent external heating be employed only when there appears y or may not be p y When no diluent is used no spontaneous increase in temperature as a consequence and lhcre has hem p y moles 0f the Phosphorus of the mixing. In most instances, the reaction is mildly halide with more than four but less than five moles of the 60 exothermic initially Whether the reaction goes to oximne cqmpoundi the Pm consists of the halo pletion without the use of extraneous heat is determined gen'flted trlorgano Phosphlte f more than a molar by the nature of the reactants. Completion of the reacequivalent of thehalogenated diorgano phosphorohalidite. tion, in any event, can be il ascertained b noting Hence, no 1solatmg procedure is required before reaction cessation in change f viscosity, refractivg index, or h with the aldehyde for preparation of the pres ntly P quantity of by-product halide. Using the lower alkanevided phosphite polyphosphonates. Notmg cessat on of carboxaldehydes, which aldehydes are generally very rechange Tefr'actwe Index or of heat evolutlon we active, external cooling is usually advantageous. When case of exothermic reactions, or of change in viscosity of working with Such active aldehvdes: optimum Conditicns the reaction mass will suflice to determine when all of the o-Ompn-se gradual addition O aldehyde to the mma'l reactants have Consumedture of phosphite and phosphorus-halogen compound with when 1S employed Wlth mufture of application of external cooling and thorough stirring. phosphorohahdite and phosphorus ester obtained from Usually it ffi to maintain the reaction temperature two moles of phosphorus trihalide and either five moles at, fr m 10 C to 50 C during addition f the or more than four but less than five moles of an alkylene aldehyde. When all or" the aldehyde has been added to oxide, the trivalent phosphorus-pentavalent phosphorus said mixture and there is no longer any evidence of exothermic reaction, completion of the reaction may be assured by heating the reaction mixture to a temperature of from, say, 50 C. to 150 C., depending upon the-nature of the reactants. With the more sluggish aldehydes, e.g., 2-phenylacetaldehyde or lauraldehyde, it may be necessary to heat the reaction mixture moderately, say, to a temperature of about 50 C. before an exothermic reaction is initiated. Employing naphthaldehyde as the aldehyde reactant and a high molecular weight phosphite and phosphorus-halogen compound, even higher temperatures may be required, e.g., temperatures of from 100 C. to 150 C. appear to give the best yields.

As stated above, formation of the desired product, i.e., the trivalent phosphorus-pentavalent phosphorus ester is accompanied by the formation of a halogenated alkane as a by-product. "Thus, the reaction of, say, bis(2-chloropropyl) phosphoroohloridite, acetaldehyde and triethyl phosphite gives ethyl chloride as a by-product:

. ll (CHzCHOlCHzOh-P-O CHP (O CH2CH3)2+CH3CH2CI CHa The lay-product halide is readily removed from the desired product by volatilization. However, in many instances, the by-product halides are articles of commerce for which many applications exist. Thus, while many currently employed processes for the, manufacture of organic compounds of phosphorus entail substantial waste of halogen in'that by-products of little commercial importance are often formed, in the present instance when starting from the phosphorus trihalide-oxirane reaction products, all of the halogen constituent of the raw materials is converted into products of economic importance.

Reaction of the phosphorus'halogen compound, the aldehydeand the trivalent phosphorus ester to give the presently useful trivalent phosphorus-pentavalentphosphorus esters is readily conducted in the presence or absence of inert diluents or solvents. The use of diluents may be particularly advantageous whenworking with the highly active aldehydes; such diluents may be, e.g., benzene, toluene, chloroform, methylene chloride or hexane.

When using substantially the stoichiometric proportion of reactants, the reaction product may be converted directly into product containing phosphorus only in the pentavalent form by heating it at a temperature of 135-225 C. The alkyl halide by-product obtained in'the halidite-aldehyde-trivalent phosphorus reaction may or may not be removed previous to this heating step. Also, if preparation of the trivalent phosphorus-pentavalent phosphorus In some instances, particularly when working with reaction products obtained from the lower molecular weight reactants, there are formed in addition to the isomerization products, small amounts of products which may result from the intermolecular condensation of the haliditealdehyde-ester product. Thus, in the case of the bis(2- chloroethy l) phosphorochloridite acetaldehydetris(2- chloroethyl) phosphite reaction product, heating at the isomerizing temperatures may result also in the following reaction: I

CH3 0 H H II A CICHQCHZPOCHIEOCHZCHZP-O HP(OCH;CH7C1)1 ClCH2CH2 OOHzCHrCl 7 00112011101 The self-condensation reaction takes place, generally, only to a limited extent. Its occurrence may be ascertained from the quantity of halide evolved during the heating step. Because, like the isomerization products, the condensation products will contain a plurality of phosphorus ester residues only in the pentavalent form,

the presence thereof in these small quantities generally will not detract from the ultimate utility of the heat reaction product. However, the isomerization product may be separated from the self-condensation product, if desired, by known isolating procedures, e.g., by molecular sieve and chromatography procedures, etc.

As disclosed in my previously referred to patent applications, the halidite-aldehyde-trivalent phosphorus reac tion products, e.g., compounds like the bis(haloalkyl) phosph'ites of a-hydroxyphosphonates obtained from a 11:1 molar ratio of the three reactants or the polyphosphorus compounds obtained when the ester is present in .aquantity which is less than equimolar, are useful for ester had been effected in the presence of a diluent, re-

it l-t lvi. lit

wherein n is zero or greater.

in the case of the 1:121 bis(2-chloroethyl) phosphorochloridite-acetaldehydetris(2 chloroethyl) phosphite reaction product the isomerization takes place as follows:

ll (CICHZCH O) P 0 C[HP (0 0112011201)? 5 H I! I CICHZCHQP 0 CH-P (O CHZOHZCI) 1 ayariety ofagricultural and industrial purposes. The presently provided compounds are useful in substantially the same fields of application; however, being more stable to hydrolysis than are the starting materials, i.e., the trivalyent phosphorus-pentavalent phosphorus esters, from which they are prepared, the presently provided exclusively pentavalent phosphorus esters will be preferred in some of these applications. The presently provided products are generally highboiling, stable materials which range from viscid liquids to waxy or crystalline solids. While the utility of the whole class of the present compounds will range somewhat with the nature of each of the three reactants, the presently provided isomerization products are generally useful as lubricant and gasoline additives, as biological and agricultural toxicants, as rubber compounding chemicals, and as adjuvant's for synthetic resins and plastics. They are very valuable as'flame-proofing agents for cellulosic and carbonaceous combustible materials generally. In applications relating to synthetic resins and plastics, the present polyphosphorus esters are surprisingly useful in that not only do they impart flame-resistant characteristics thereto, but they also frequently demonstrate plasticizing and stabiliZing. They are compatible over a wide concentration rangewith a great variety of resinous materials. They are advantageously employed in the preparation of improved synthetics such as the phenolic, polyester, polyamide, and cellulose ester resins, in the vinyl polymers such as polyvinyl chloride, the polyvinyl acetals, polystyrene, polyethylene, vinyl chloride-vinyl acetate copolymers, olefin-maleic anhydride copolymers, polybutadiene and the copolymer elastorners such as butadiene-styrene or butadiene acrylonitrile copolymers, etc. They are also very effectively used in the preparation of foamed resins, e.g., polystyrene foam or of polyester foams, such as polyethylene terephthalate, or the polyurethanes. Thus, use of the polyphosphorus compound with the required diisocyanate component and required hydroxy component in a quantity of, say, up to 40% or even 50% of the mix gives foamed products which not only are flame-proofed but which also have been compatibly plasticized.

Many of the presently provided products, particularly those that contain a plurality of the pentavalent phosphorus ester groups, are useful as functional fluids in electrical and force-transmitting applications. Being stable at high temperatures, substantially unaffected by moisture and either acidic or alkaline agents, and remaining liquid over a wide range of temperature conditions, they are generally useful in force-transmitting applications, e.g., as lubricants, as antifreeze compositions and as hydraulic fluids. They can be used alone for such purposes or mixed with other materials known in the art to be effective for these purposes, e.g., partially chlorinated biphenyls, alkylated polystyrenes, polyacrylates, etc. The present products are also useful as modifying agents for hydrocarbon oil lubricants, e.g., as lubricity improving agents.

Those of the presently prepared compounds which are gasoline-soluble are particularly useful as stable preignition additives for leaded gasolines. The invention thus provides an improved fuel for spark ignition internal corn bustion engines which consists essentially of gasoline, an organo lead anti-knock and the gasoline-soluble isomerization product, said product being present in said fuel in a quantity sufiicient to suppress preignition of the fuel.

Preignition is the ignition of the combustible mixture of air and fuel prior to firing by the spark plug. This occurs when deposits of readily glowing material build up in the combustion chamber. When the fuel is a gasoline containing an organolead anti-knock together with a halohydrocarbon scavenger, such readily glowing deposits comprise carbon in a mixture with lead halides; the latter acting to reduce the normal ignition temperature of carbon. Since reduction of the ignition temperature tends to increase with increasing concentration of the organolead anti-knock, preignition is a problem which becomes particularly troublesome as use of high compression engines become more prevalent. The deposits of carbon and lead salt retain sufficient heat from the previous firing cycle in enough quantity to permit them to glow, and if the glowing period (which depends on ease of ignition, and hence the lead content of the deposit) is long enough, the fuel is fired in the next cycle before it can be fired by the spark plug. The erratic firing which thus results is demonstrated by a wild ping or a dull, thudding knock. It is generally accompanied by increased detonation, sparkplug fouling, and reduction of exhaust valve life.

It has now been found that preignition and the various difficulties consequent thereto can be substantially suppressed or entirely eliminated by incorporating the gasoline-soluble pentavalent dior polyphosphorus compound into the leaded gasoline in a preignition-inhibiting quantity. Such a quantity, of course, will depend upon the content of organolead compound and halohydrocarbon scavenger in the fuel. Leaded gasolines usually contain an anti-knocking quantity of an organolead compound CHaCHClCHrO-li CHP such as tetraethyllead, tetramethyllead, dirnethyldiethyllead, and tetraphenyllead and substantially the amount of hydrocarbon halide scavenger, say, ethylene dibromide, ethylene dichloride, acetylene tetrabromide, or monoor polyhalopropane, butane, or pentane, or polyhaloalkyl benzene, which is calculated to react with the organolead compound to give a lead halide, e.g., lead bromide when the organolead compound is tetraethyllead and the halohydrocarbon is ethylene dibromide. The quantity of the present compound which will suppress preignition of the leaded hydrocarbon fuel will depend upon the quantity of lead present in the fuel.

The invention is further illustrated by, but not limited to, the following examples.

Example 1 This example describes the production of a phosphitediphosphonate by reaction of acetaldchyde with a mixture of phosphite and phosphorochloridite prepared from two moles of phosphorus trichloride and 4.67 moles of propylene oxide, and isomerization of the phosphite-diphosphonate to the triphosph onate.

The mixture of phosphite and phosphorochloridite was prepared as follows: A 2-liter flask was charged with 550 g. (4.0 moles) of phosphorus trichloride and 4.1 g. (0.05 mole) of ethylene chlorohydrin. It was immersed in a Dry Ice bath and 539 g. (9.28 moles) of propylene oxide was added thereto during 0.4 hour at a temperature of 1015 C.

After removing a 6.0 g. sample of the resulting reaction mixture, the remaining reaction product, consisting of one mole of tris(2-chloropropyl) phosphite per two moles of bis(2-chloropropyl) phosphorochloridite was treated with 129 g. (2.94 moles) of acetaldehyde during 0.2 hour at a temperature of 15-30 C. When the heat of reaction had subsided (about 0.2 hour after addition of the aldehyde), the reaction mixture was warmed at 55S5 C. for 0.75 hour. A 5.0 g. analytical sample was removed and the remainder was concentrated to a pot temperature of 142 C./0.3 mm. to give 300.2 g. (99% theoreticai yield) of propylene dichloride in a Dry Ice trap and as residue 901 g. (100% theoretical yield) of phosphite-diphosphonate, 11 1.4803, of the formula i ll ll P-O lH P (O CHzCHClCHa):

wherein n has an average value of 1. Cryoscopic molecular weight determination of the product in benzene gave a value of 658 as compared to 680, the theoretical value. Nuclear magnetic. resonance spectra for phosphorus showed characteristic chemical shifts at minus 141.6 ppm. (relative to H PO for the trivalent phosphorus and at The minus 21.5 ppm. for the pentavalent phosphorus. product analyzed as follows:

Found Caled. for

CwilssClsOgPz Percent C 33. 32 33. 5

26.08 26.1 Percent 1 3.68 13.7

A 300 g. sample of the above phosphite-diphosphonate was isomerized to the triphosphonate by heating at 190- 200 C. for 0.5 hour. The reaction mixture was cooled to C., and finally concentrated to C./ 0.05 mm. to give 5.4 g. of by-product propylene dichloride in the Dry Ice trap and as residue 294.2 g. (98% theoretical yield) of the triphosphonate of the formula 0 CHa 0 CH3 0 II I CHzOl 25 26 where n has an average value of 1. Crysocopic molecutris(2-'chloropropyl) phosphite and bis(2-chloropropyl) lar weight determination of the product in benzene gave phosphorochloridite in a one to three molar ratio. a value of 713 as compared to 680, the theoretical value. Nuclear magnetic resonance study of the mixture gave Nuclear magnetic resonance spectra for phosphorus a characteristic chemical shift of minus 168.5 ppm. (relashowed that it had been completely converted to the pentive to H PO for the phosphorochloridite and minus tavalent state. It analyzed as follows: 141.8 p.p.m. for the phosphite.

To the mixture of phosphite and phosphorochloridite Found fi gg there was added, during minutes, 145 g. (3.3 moles) of 3B 5 g a acetaldehyde. During addition of the aldehyde, the tem- Percent G 33 Q9 335 10 perature of the reaction mixture was maintained at Percent :1: 5'72 5, 6 C. by cooling, and it was maintained at this temperag r gz 3 g? V ture for an additional 0.5 hour after all of the aldehyde e ce had been added. At the end of this period, no further heat of reaction was evidenced, and in order to determine Example 2 15 whether all of the chloridite had reacted, another 5.0 g. This example shows preparation of a phosphite-diphosportion of acetaldehyde was added. A 1.0 C. temperaphonate by reaction of a phosphorochloridite and an aldeture rise was noted; but the addition of another 5.0 g. of hyde with a previously prepared phosphite of a hydroxythe aldehyde caused no temperature change. The color alkylphosphonate, and isomerization of the phosphitefiless reaction mixture was then warmed at 8590 C. for pho phonate to the triphosphonate. 20 0.5 hour to assure complete reaction. By-product propyl- The bis(Z-chloropropyl) phosphite of bis(Z-chlOrO- ene dichloride was removed by placing the mixture under propyl) 1-hydroxyethylphosphonate was prepared by reac vacuum and concentrating, with stirring, to a pot temperation of acetaldehyde with an equimolar mixture of bis(Z- ture of 125 C./0.5 mm. There was thus obtained as chloropropyl) phosphorochloridite and tris(2--chloropr0py residue 890.0 g. of a polyphosphonate-phosphite of the phosphite. To 248 g. (0.5 mole) of this compound there formula was first added 126.8 g. (0.5 mole) of bis(Z-chloropropyl) wherein n has an average value of 2.

phosphorochloridite and then there was introduced during A 301 g. portion of the polyphosphonate-phosphite a time of 0.2 hour, 26.4 g. (0.5 mole plus 20% excess) of was transferred to a flask equipped with a condenser, and acetaldehyde while maintaining the temperature of the it was isomerized by stirring and heating under vacuum reaction mixture at 25-35 C. by cooling. The whole was to 195 C./0.02 mm. and maintaining it at 195 then warmed to 80-90" C. for 0.3 hour and then concen- C.-205 C./ 0.02 mm. for 0.5 hour. There was obtained, trated to 142 C./0.2 mm. to give 58.4 g. of distillate in as a colorless liquid residue, the phosphite-free polyphosthe trap which formed a part of the reaction equipment phonate of the formula.

I: l ii] I i Y CH3CHC1CHzO-P- -0CH POCHP(OCHCHC1OH3)1 ClCHzCJHLCHaCHCICHr-j I (theory is 56.5 g. of by-product propylene dichloride plus wherein n has an average value of 2. 4.4 g. excess acetaldehyde), and 340.9 g. (100% theoretical yield) of the phosphite-polyphosphonate, 11 1.4807, of Example4 the structure This example is like Example 1 except that the phos- CH; 5 0 on; (CHsCHClCHzO)2P[OlH-jlO-JH-l (OCHzCHClCHQ OHSCHCICHZO 11 wherein n has an average value of 1. phorus trichloride and the propylene oxide were employed Heating of the phosphite-diphosphonate as in Example in a 2:475 ma 1 av th t' h h t.

g e e mp Osp ona e Propylene oxide (552 g., 9.5 moles) was added, during 20 minutes, to a mixture consisting of 550 g. (4.0

oles of h h t 'd chloropropyl)phosphite and bis(2-chloropropyl)phosm p 05p oms nchlon e and 275 g of ethylene phorochloridite y reacficn of two moles of phosphorus 6O chlorohydrin while maintaining the temperature of the trichloride with 4.5 moles of propylene oxide, subsequent reactlon mlxture at 10400 (largely 15*200 A Example 3 This example shows preparation of a mixture of tris(2- reaction of said mixture with acetaldehyde to obtain a Sample Was removed analysis- O e condensate containing a plurality of phosphonate radicals mainder of the reaction mixture, which consisted essenand a Single PhOSFhite P, and isomelizatlon to a P tially of a mixture of tris(2-chloropropyl) phosphite and not having a plurality of phosphonate radicals and no phosphite group.

A reaction vessel equipped with stirrer, thermometer, a

bis(2-chloropropyl)phosphorochloridite, there was added 127 g. of acetaldehyde, during 5 minutes, while maintainprotected water condenser and a protected dropping funnel ing i tempferature of the reaction P F at 18-200 was swept with nitrogen and then charged with 55 by mild cooling. The colorless reaction mixture was then (4.0 moles) of phosphorus trichloride and 2.75 g. of ethylwarmed at 90 Cffor 0.5 hour, placed under vacuum ene chlorohydrin. The vesselwas cooledina Dry Ice bath and concentrated to a pot temperature of as 522 g. (9.0 moles) of propylene oxide was added, duringzo minutes at a temperature M C (largely mm. to remove by product propylene dichloride. There 15-20 C.). The colorless reaction mixture was stirred was thus obtained as residue 3- of the colorless for 0.5 hour to obtain a mixture consisting essentially of 75 liquid reaction product, 11 1.4797, of which two-thirds where n is 1.

This mixture, which has an average atomic ratio of C H Cl O P analyzed as follows Found Caled. for

ClElH26Cl3-5OGP2 Percent C 33.77 33. 65 Percent H- 5.83 5. 65 Percent 01. 26. 62 26.75 Percent P 13. 33 13.36

A 300.5 g. portion of the reaction product was transferred to a flask equipped with a condenser, and it was heated under vacuum with stirring to 195 C./0.2 mm. and maintained at 195-205 C./0.2 mm. for 0.5 hour. There was thus obtained as residue the substantially phosphite-free product.

Hydrolytic stability of the presently obtained products were conducted by adding 250 m1. of carbon dioxide- Eree distilled water to 25 g. of the test compound, stirring the resulting mixture for 24 hours, and titrating with 0.1 N alcoholic sodium hydroxide in the presence of alcoholic thymol blue indicator. For purposes of comparison, the same test was conducted on the 1:1:1 halidite-aldehyde-phosphite reaction product:

(OHgOHClCHzOhPOCHi (OCH2CHClOHa)z The results, reported as milliequivalents of NaOH/g. of sample, are shown below:

1:1:1 pro 0.816 Phosphite-contg. product, this example 0.465 Phosphite-free product, this example 0.193

Example This example is like Example 4 except that it was conducted on a large scale in the pilot plant.

The reaction mixture, comprising the polyphosphonatephosphite, analyzed as follows:

Found Calcd. for

Percent C 33. 56 33. 65 Percent I-I. 5. 81 5.65 Percent 01 26. 59 26. 75 Percent P 13. 39 13. 36

Hydrolytic stability of said reaction mixture, determined as in Example 4, gave a value of 0.402 milliequivalent of NaOH/ g. sample.

A 1500 g. portion of said reaction mixture was isomerized to the phosphonate as follows: It was placed in a 2-liter flask and heated, with stirring to about 170 0, whereby a mild exothermic reaction occurred, and the temperature of the reaction mixture remained at 180- 188" C. for 0.2 hour without external heating. It was then heated at 190-200 C. for 0.5 hour, cooled to 160 C. and placed under a vacuum of 0.1 mm. Hg pressure as it was allowed to cool. There was thus collected 30.9 g. of propylene dichloride in the Dry Ice trap which formed a part of the equipment, and as 25% residue, 1471 g. (98% theoretical yield) of the phosphite-free product. Testing of the hydrolytic stability P-O CH-F (O CHzCHClCHa):

thereof, using the method described in Example 4, gave a value of 0.186 milliequivalent of NaOH/ g. Nuclear magnetic resonance spectra for phosphorus showed only chemical shifts at -26.0 p.p.m. and 20.8 ppm, both characteristic of pentavalent phosphorus of the phosphonate type. There was no evidence of the presence of trivalent phosphorus in the product.

Example 6 This example describes reaction of two moles of phosphorus trichloride with 4.5 moles of ethylene oxide to obtain a mixture of tris(2-chloroethyl) phosphite and bis(2-chloroethyl) phosphorochloridite, subsequent reaction of said mixture with acetaldehyde to obtain a polyphosphonate-phosphite, and isomerization of the latter to the phosphite-free product.

To 1100 g. (8.0 moles) of phosphorus trichloride and 8.3 g. of ethylene chlorohydrin there was added 793 g. (18.0 moles) of ethylene oxide during 0.75 hour while maintaining the temperature of the reaction mixture at 10-20 C. (largely l015 C.). A 6.0 g. sample was removed for analysis and to the remaining mixture of tris(2-chloroethyl) phosphite and bis(2-chloroethy1) phosphorochloridite there was added 290 g. (6.6 moles, 10% excess) of acetaldehyde during 0.3 hour while maintaining the temperature of the reaction mixture at 2530 C. by cooling. When all of the acetaldehyde had been added, cooling was discontinued, and the temperature of the reaction mixture increased spontaneously to 52 C. The mixture was then warmed at 85-90" C. for 0.5 hour, cooled to 30 C. and then concentrated to a pot temperature of 110 C./1 mm. to give 553.5 g. of ethylene dichloride in the Dry Ice trap and as residue a polyphosphonate-phosphite of the formula O I If] u (CICEZCHzOMP -OCII POCHP(OCH2CH:CI):

(CICHZCHzOhPO?H%(OCII3CH CD3 Conversion of the polyphosphonate-phosphite to the phosphite-free product was conducted by heating it at 190 C.-2'00 C. for 0.5 hour and concentrating to C./0.5 mm. There was thus obtained the polyphosphonate, 21 1.4927, of the formula 1 F i u l ClCHzCHzO-IiOCH--I O(IJH1(00112011201):

ClCH CHg OIGHQGHQOJB CH3 Example 7 This example shows the preparation of a phosphitepolyphosphonate from two moles of phosphorus trichloride and 4.5 molesof ethylene oxide and acetaldehyde as in Example 6 and then distillation of the by-product ethylene dichloride as the product was heated for conversion to polyphosphonate.

A mixture of tris(2-chloroethyl) phosphite and bis(2- chloroethyl) phosphorochloridite was prepared by adding 793 g. (18.0 moles) of ethylene oxide to a mixture consisting of 1100 g. (8.0 moles) of phosphorus trichloride and 8.2 g. of ethylene chlorohydrin with cooling at C. (largely 10-15" C.) during 1.25 hour.

After removing a 6.0 g. sample from the reaction product, the remainder, which consisted of tris(2-chloroethyl) phosphite and bis(2-chloroethyl) phosphorochloridite in a 1:3 ratio, was treated with 290 g. (6.6 moles, 10% excess) of acetaldehyde at 20-30 C. during 0.2 hour. Cooling was applied to maintain this temperature during addition of the acetaldehyde and for another 0.7 hour after the aldehyde had been added. The reaction temperature was finally allowed to increase spontaneously to 41 C. The resulting reaction mixture consisted of an ethylene dichloride solution of the polyphosphonatephosphite of the formula CH: O (onioiouzoni oc11-i O H O (IJHP (OCHzCHzCl):

where n has an average value of 2. Nuclear magnetic resonance measurements on this product showed a characteristic chemical shift of 142 p.p.m. relative to H PO for the trivalent phosphorus and of -22 p.p.m. for the pentavalent phosphorus.

The above polyphosphonate-phosphite was isomerized to the phosphite-free compound as the by-product ethylene dichloride was distilled and the residue was finally heated at 195-201" C. for- 0.3 hour, whereby 584 g. of ethylene dichloride was collected. The residue was cooled to 150 C. and then concentrated to 160 C./0.2 mm. to give an additional 45.0 g. of ethylene dichloride and as residue 1571 g. of the polyphosphonate of the formula l l OCHgCHgCl n H l li cromcmo-P-oCn-r ClCHzCHzL Example 8 This example shows preparation of a polyphosphonatephosphite by reaction of 1.75 moles of acetaldehyde with a mixture of tris(2-chloropropyl) phosphite and bis(2- chloropropyl) phosphorochloridite prepared by reacting two moles of phosphorus trichloride with 4.25 moles of propylene oxide, and conversion of the polyphosphonatephosphite to the phosphite-free product.

To a mixture consisting of 550 g. (4.0 moles) of phosphorus trichloride and 2.75 g. of ethylene 'chlorohydrin there was added, with cooling during 0.4 hour, 493 g. (8.50 moles) of propylene oxide. About the first two thirds of the oxide was added at a temperature of 5-15 C. and the last one-third at 0-5 C. A 9.0 g.' sample of the resulting reaction mixture was removed for analysis and the residual mixture, consisting essentially of tris(2- Found Calcd. for

C22 44C1sO12P4 Percent C 33. 35 33.0 Percent H- 5. 53 5. 54 Percent 01 22. 59 22.1 Percent P 15. 06 15. 5

Testing of the hydrolytic stability of the presently prepared polyphosphonate-phosphite as described in Example 4 gave a value of 0.392 milliequivalent NaOH/g. sample.

Conversion of the polyphosphonate-phosphite to the phosphite-free product was effected by heating as in Example 7.

Example 9 This example describes the preparation of a polyphosphonate-phosphite by reacting two moles of phosphorus trichloride with 4.75 moles of propylene oxide to obtain a mixture of tris-(Z-chloropropyl) phosphite and -bis(2- chloropropyl) phosphorochloridite and subsequent reaction of said mixture with formaldehyde. 1

To a cooled mixture consisting of 550 g. (4.0 moles) of phosphorus trichloride and 2.75 g. of ethylene chlorohydrin there was added, during 0.4 hour, 552 g. (9.5 moles) of propylene oxide while maintaining the temperature of the reaction mixture at 1220 C. A 6 g. sample of the reaction mixture was removed. The remaining mixture of tris(2-chloropropyl) phosphite and bis(2-chloropropyl) phosphorochloridite was warmed to C., and 150 g. of formaldehyde was distilled into said mixture during 1.25 hour while maintaining the temperature of the reaction mixture at -65 C. by occasional cooling. The residue was then distilled to a pot temperature of 150 C., placed under vacuum and concentrated to a pot temperature of 160 C./ 0.05 mm. to give as residue 918 g. of the colorless, liquid reaction mixture of which two-thirds in moles consisted of a polyphosphonatephosphite of the formula 0CHzl OCHzi (OCHICHCICHZ)! CHACHCICH: In

Where n is l.

A 502 g. portion of said reaction mixture was placed in a 500 cc. flask, stirred and heated to 200 C. and then maintained at 195200 C. for 0.5 hour. After allowing it to cool to C., it was concentrated to C./0.05 mm. to give 12 g. of by-product which collected in the Dry Ice trap that formed a part of the equipment and 488 g. (97% recovery) of product wherein the phosphorus was present only as phosphonate. Testing of the hydrolytic stability of the present product as described in Example 4 gave a value of 0.322 milliequivalent of NaOH/ g. sample.

Example 10 This example shows reaction of a mixture of phosphorochloridite, phosphite and aldehyde wherein there is employed a very large excess of chlorodite and aldehyde with respect to the phosphite.

CH: 1 ll r l ClCHzCHP-CH CHJCHClCIIZ l. CHtoHoHi0 ln where n has an average value of 10.

Example 11 A polyphosphonate having dissimilar alcohol residues was prepared as follows:

To a solution consisting of 16.5 g. (0.065 mole) of bis(2 chloropropyl) phosphorochloridite and 5.4 g. (0.0325 mole) of triethyl phosphite in 30 ml. of methylene chloride there was added durin.g0.l hour 3.8 g. (0.065 mole) of propionaldehyde while maintaining the temperature of the reaction mixture at 30 C. by cooling. When the heat of reaction had subsided (about 0.1 hour after all of the aldehyde had been added), the mixture was warmed at reflux for 0.5 hour, distilled to a pot temperature of 70 C., and then concentrated to 107 C./0.02 nun. to obtain the phosphite-polyphosphonate, n 1.4696.

After removing a 4.7 g. sample of the phosphite-polyphosphonate for analysis, the residue was converted to the phosphite-free product by heating it at 190-l95 C. for 0.2 hour and then concentrating to 170 C./ 0.05 mm. to give 15.0 g. (99% theoretical yield) of the colorless, liquid polyphosphonate, r2 1.4715, of the formula:

CHaCHClCHrA CH3CI'ICICH2 Example 12 Bis(2-chloropropyl) phosphite of bis(2-chloropropyl) 1-hydroxyethylphosphonate was prepared by reaction of an equirnolar mixture of tris(2-chloropropyl) phosphite and bis(2-chloropropyl) phosphorochloridite with acetaldehyde. A 426.5 g. portion was isomerized to the diphosphona-te by heating at 190 C. to 205 C. for 0.75 hour. Concentration to 165 C./0.02 mm. gave 411.5 g. (97% theoretical yield) of the substantially pure diphosphona-te, n 1.4788, of the formula CHaCHClCH: CH3

(MezCHO CHzOHClCI-Iz0)gP was prepared by the process described in my application, Serial No. 780,209, filed December 15, 1958, by adding acetaldehyde to a substantially equimolar mixture of tris- (2-chloroethyl) phosphite and bis(2-chloroethyl) phosphorochloriditc with cooling and removing by-product propylene dichloride from the resulting reaction mixture.

Isomerization of the above phosphite-phosphonate to the phosphite-free product was effected by placing 31.78 g. thereof in a 5-liter flask, stirring and warming with a mantle to 165175 C. whereby a mildly exothermic reaction appeared to be initiated, maintaining the reaction mixture at 180-200 C. for 0.5 hour, at 195200 C. for another 0.5 hour, cooling to 150 C. and finally concentrating to 170 C./0.2 mm. to give as residue a 97.5% theoretical yield of the phosphite-free phosphonate, 11 1.4913 of the formula Testing of the hydrolytic stability of the presently prepared diphosphonate gave a value of 0.149 milliequivalent NaOH/ g. sample as compared to 1.852, the value for the unisornerized phosp-hite, i.e., the bis(2-chloroethyl) phosphite of bis(2-chloroethyl) l-hydroxyethylphosphonate. In both instances the hydrolytic stability tests were conducted as described in Example 4.

Example 14 This example describes the preparation of phosphitefree polyphosphonate by reaction of two moles of phosphorus trichloride with 4.8 moles of 1,2-epoxy-3-isopropoxypropane to obtain a mixture of phosphite and phosphorochloridite, reaction of said mixture with undecaldehyde to obtain the polyphosphonate-phosphite, and heat treatment of the latter to form the phosphite-free product.

To a mixture consisting of 49.2 g. (0.358 mole) of phosphorus trichloride, 0.5 g. of ethylene chlorohydrin and ml. of methylene dichloride there was gradually added, during 0.2 hour, 100 g. (0.860 mole) of 1,2-epoxy- 3-isopropoxypropane while cooling the reaction mixture to maintain the temperature thereof at 2030 C. The whole was then maintained at 2530 C. for 0.2 hour and subsequently warmed at reflux for 0.3 hour. After removing a 5.0 g. sample of the reaction product for analysis, the remaining mixture of tris(2-ehloro-3-isopropoxypropyl) phosphite and bis(2-ehloro-3-isopropoxypropyl) phosphorochloridite was treated with 36.6 g. (0.215 mole) of n-undecanal during about 5 minutes at 3547 C. The resulting reaction mixture was warmed at reflux for 1.0 hour, concentrated at water-pump pressure to C., and finally to C./1.0 mm. to give as residue 159.8 g. of a phosphite-phosphonate product of which two-thirds in moles consisted of the polyphosphonate-phosphite of the formula CHCl where Me is the methyl radical and n has an average value of 1.

Evaluation of hydrolytic stability of the presently provided polyphosphonate-phosphite employing the procedure described in Example 4 gave a value of 0.539 milliequivalent or" NaOH/g. sample.

A 75 g. portion of the above phosphite-phosphonate product was heated with stirring at 200 C. for 0.25

hour, cooled to 130 C. and then concentrated to 160 C./0.2 mm. to give 71.5 g. of the phosphite-free product. Testing of the hydrolytic stability thereof by the procedure described in Example 4 gave a value of 0.290 5 milliequivalent of NaOH/g. sample.

(CsHsO OHaCHGlCHaOhP I- Example This example describes the preparation of a polyphosphonate-phosphite by the reaction of two moles of phosphorus trichloride With/1.8 moles'of butadiene monoxide to obtain a mixture of phosphite and phosphorochloridite and reaction of said mixture with propionaldehyde.

To a cooled (10-15 C.) mixture consisting of 274.7 g. (2 moles) of phosphorus trichloride and 2.7 g. of ethylene chlorohydrin there Was added, during 0.3 hour, 336 g. (4.8 moles) of butadiene monoxide. A 5.5 g. sample of the reaction mixture was removed and to the remaining mixture of tris(2-chloro-3-butenyl) phosphite and bis(2-chl0ro-3-butenyl) phosphorochloridite there was added 101.5 g. (1.75 moles) of propionaldehyde during 0.3 hour at a temperature of -35 C. The whole was then warmed to 70 C. and concentrated to 102 C./4.0 mm. to give as residue 562.5 g. of phosphite-phosphonate product, of which two-thirds in moles consisted of the polyphosphonate-phosphite of the formula aJH Where Et is the ethyl radical and n is 1.

A 300 g. portion of said phosphite-phosphonate product was heated to 182 C.- and then concentrated to 185 C./0.5 mm. to give 271.5 g. of the phosphite-free polyphosphonate. Testing of the hydrolytic stability of this product by the procedure of Example 4 gave a value of 0.184 milliequivalent of NaOH/g. samplewhereas like testing of said phosphite-phosphonate product previous to the isomerization step gave a value of 0.996.

34 at 35-50" C. by cooling. The whole was then warmed at reflux for 0.5 hour and concentrated to 115 C./ 2 mm. to give as residue 558 g. of a mixture of by-product 2,3- dichloropropyl phenyl ether and phosphite-phosphonate product of which in moles consisted of the polyphosphonate-phosphite product of the formula Et 0 Et I II I II OCH-1' OCH-P (O CHzCHClCHzO C513 CtH OOHgCHClCHz n Where Et is the ethyl radical and n is 1.

A 300 g. portion of said mixture was heated to 200 C. and then concentrated to 200 C./1 mm. to give 66.5 g. of by-product, 2,3-dichloropropyl phenyl ether and as residue 226.7 g. of the phosphite-free polyphosphonate.

Example 17 V This example describes preparation of a phosphite-free phosphonate product by reaction of two moles of phosphorus trichloride with 4.8 moles of ethylene oxide to obtain a mixture of phosphite and phosphorochloridite, reaction of said mixture with furfural to give the polyphosphonate-phosphite andconversion of the latter to the phosphite-free polyphosphonate.

To a mixture consisting of 1100 g. (8.0 moles) of phosphorus trichloride and 8.2 g. of ethylene chlorohydrin there was introduced, during 1.2 hour, 845 g. (19.2 moles) of ethylene oxide at 1020 C. To one-half (973 g.) of the resulting mixture of tris(2-chloroethyl) phosphite and bis(2-chloroethyl) phosphorochloridite there was added 231 g. (2.4 moles) of furfural during 0.2 hour. The Whole was then warmed to 90 C. whereupon an exothermal reaction occurred and cooling was required to maintain the temperature of the reaction mixture at 8595 C. for 0.5 hour. It wa finally warmed at 100-105 C. for 0.5 hour and concentrated to 100 C./2 mm. to give as residue a phosphite-phosphonate product of which 50% consisted of a phosphonate-phosphite of the formula 0 0 crnomol o s l n (ClCH CH O) P-OCHP oonmoomorncn,

ll R i it CH-CH n CH--CH Example 16 where n is 1.

This example describes preparation of a phosphite free polyphosphonate by reaction of two moles of phosphorus trichloride with 4.8 moles of 1,2-epoxy-3-phenoxypropane, reaction of the resulting mixture of phosphite and phosphorochloridite with propionaldehyde, to obtain a polyphosphonate-phosphite, and conversion of the latter to give the phosphite-free product.

To a mixture consisting of 137.3 g. (1.0 mole) of phosphorus trichloride, 1.5 g. of ethylene chlorohydrin and 200 ml. of methylene dichloride there was added, during 0.25 hour, 360 g. (2.4 moles) of 1,2-epoxy-3- phenoxypropane. The temperature of the reaction mixture increased spontaneously to reflux (pot temperature of 58 C.) during the addition, and subsequent heating of the reaction kept the mixture at reflux for 1.5 hour. To the resulting reaction mixture, comprising tris(2- chloro-3-phenoxypropyl) phosphite and bis(2-chloro-3- phenoxypropyl) phosphorochloridite, there was added 71.8 g. (1.24 moles) of propionaldehyde during 0.2 hour while maintaining the temperature of the reaction mixture;

A 300 g. portion of said phosphite-phosphonate product was heated to 195 C. and then concentrated to 180 C./0.5 mm. to give asresidue 293 g. (98% theoretical yield) of the phosphite-free polyphosphonate.

Example 18 maintaining the temperature of the reaction mixture at 3040 C. The whole was then warmed to C. and concentrated to 102 C./0.3 mm. to give 59.5 g. of ethylene dichloride in the Dry Ice trap which formed a part of the reaction equipment and as residue a phosphitephosphonate product of which 50% in moles consisted of the polyphosphonate-phosphite of the formula where n is 1, and

I! II GlCHzCHz--POCH-P 033011201),

0 (CICILCH 0) P O oHI 0oHi (o CH CH 01 5 CICHZCHF CHZCHfl 2 7 l 2 2 z Hydrolytic stability of this product determined ac- 033105130113 cording to the procedure described in Example 4 gave OH; OH, a value of 0.641 milliequivalent of NaOH/g. sample $11201 as compared to 1.930, the similarly obtained value for 10 the phosphite-phosphonate product previous to the isom- CH; 1 erization step. where n is 1. 1 f d I h h E l 20 7 g. samp e o sai hos hiteos onate roduct was removed for analysis, and the r mai rider was heated T i exampl? 1S hke Example 19 except that dlfferem to 200 C., cooled to 140 C., and then concentrated to hahdlte and eser.are used 165 C./0.3 mm. to give as residue 219 g. of the phos- To 2 9 mixtureponslstmg' of 1100 moles) phite-free product of which 50% in moles consisted of of P1}0Spnorus trichloride of ethylene chloro' the diphosphonate hydnn there was added, dur1ng 0.8 hour, 1 136 g. (19.6

moles) of propylene oxide while maintalnmg the tem- 20 perature of the reaction mixture at 10-20 C. (largely CICHIOEPPwO(fHWPwCHICHQCW 10l5 C.). A 6.5 g. sample of the reaction mixture on, was removed and to the remaining mixture of tris(2- (lJH, E chloropropyl) phosphite and bis(2-chloropropyl) phosphorochloridite there was added during 0.25 hour, 011101 246.6 g. (4.4 moles) of acrolein while maintaining the CH3 temperature of the reaction mixture at 24-30 C. by and 50% in moles of the polyphosphonate cooling. When cooling was discontinued the temperature of the reaction mixture increased spontaneously to l l H 41 C. It was then heated to 103 C. and maintained momcm-r OCHPOCHP(OCH:CH:C1): at 85-103" C. for 0.75 hour. Concentration of the (H12 resulting mixture to 120 C./1 mm. gave 455.5 g. of l l l by-product propylene dichloride, which collected in the E Dry Ice trap forming part of the equipment, and as CHQCI s CHzCl S residue a phosphonate-phosphite product, of which two- 5 A thirds in moles consisted of the polyphosphonate of the in which n is 1. formula CH=OH2 I J; (I) i CH=OH (CH;CHC1CH1O)zP--O H1 OCHfi(OCH;CHC1CHz):

l. homcnolomln 0 Example 19 where n is 1.

This example describes preparation of a phosphitefree phosphonate using acrolein as the aldehyde.

To 486.5 g. of the mixture of tris(2-chloroethyl) phosphite and bis(2-chloroethyl) phosphorochloridite prepared in Example 16 there was added 70.6 g. of acrolein during one hour while maintaining the temperature at 1020 C. by cooling. The whole was then warmed to 90 C. and concentrated to 140 C./0.3 mm. to give 437 g. of a phosphite-phosphonate product of which in moles consisted of the polyphosphonate-phosphite of the formula 1 till.

A portion of said phosphonate-phosphite product was heated to about 185 C. at which point an exothermic reaction slowly increased the temperature to 200 C. Heating was continued at 185-200 C. for 0.5 hour. The reaction mixture was then cooled to 140 C., placed under vacuum and concentrated to a pot temperature of 167 C./1 mm. to give as residue the phosphite-free phosphonate. Hydrolytic stability of this product determined according to the procedure described in Example 4 gave a value of 0.608 milliequivalent of NaOH/g. sample as compared to 1.570, the similarly obtained value for the unisomerized product, i.e., the phosphonate-phosphite product previous to the heating step.

Example 21 This example discloses the use of an aldehyde ester in the preparation of a phosphite-free phosphonate.

To 72 g. of a mixture of tris(2-chloroethyl) phosphite and bis(2-chloroethyl) phosphorochloridite prepared by the reaction of two moles of phosphorus trichloride with 4.8 moles of ethylene oxide there was added with ice cooling in one portion, 19.5 g. (0.15 mole) of ethyl 3- formylpropionate. The temperature of the reaction mixture increased spontaneously from 28 C. to 52 C. When there was no further evidence of exothermal reaction, the mixture Was warmed to 83 C. and then concentrated to a pot temperature of 122 C./0.6 mm. to give 13.4 g. theoretical yield) of by-product ethylene dichloride in the Dry Ice trap and 78.5 g. of

37 the phosphite-polyphosphate, 11 1.4863, of which 50% In moles consisted of the formula ClCH CH: L CIOH CHZJLL where n is l, and the remainder consisted essentially of the diphosphonate of the formula To a mixture consisting of 716 g. (4.0 moles) of phenylphosphonous dichloride and 7.1 g. of ethylene chlorohydrin there was added 336 g. (5.8 moles) of propylene oxide during 0.25 hour while maintaining the temperature of the reaction mixture at -5 C. by means of Dry Ice cooling. The reaction was rapid, very exothermic, and was complete by the time all of the propylene oxide had been added. A 7.0 g. sample of the reaction product was removed for analysis and to the remaining reaction product, consisting of 2-chloropropyl phenylphosphonochloridite and bis(2-chloropropyl) phenylphosphonite, there was added, during 0.2 hour, 107 g. (2.42 moles) of acetaldehyde. Moderate cooling was employed to keep the temperature below 32 C. during the addition of the aldehyde and for about 0.25 hour after all of the aldehyde had been added. The colorless, viscous reaction mixture was then warmed at 55-65 C. for one hour and then concentrated to 90 C./1 mm. to give 207.5 g. of the by-product propylene dichloride in the Dry Ice trap which formed a part of the reaction equipment and as residue 946.5 g. of a phosphonite-phosphinate product, 11 1.5478, of which 22% in moles consisted of the polyphosphorus compound of the formula Isomerization of the trivalent phosphorus ester radical in said phosphonite-phosphinate was effected as follows. A 300 g. portion of the product was heated to (OHgClCHCICHEO) P an. 0 01130 on: 0 our.

\11 I I ll I P--ooH-1 OCH-P-OGH CHClCHa oiomi vn hind.

CHI

, ll 0 HPO (IDHP (O CHzCHzCl):

CHZOHQC OQCHICHI where n is 1, and of the compound CICHg-CH Nuclear magnetic resonance spectra for phosphorus showed a chemical shift only at -38.0 p.p.-m. which is characteristic of phosphinates of this type.

Example 23 This example describes the preparation of a phosphitefree polyphosphonate by reacting two moles of phosphorus trichloride with 4.9 moles of epichlorohydrin to obtain a mixture of phosphite and phosphorochloridite, reacting said mixture with acetaldehyde to obtain the polyphosphonate-phosphite and converting the latter to the phosphite-free product.

To a mixture consisting of 413 g. (3.0 moles) of phosphorus trichloride and 4.1 g. of ethylene chlorohydrin there was added, during 0.4 hour, 680 g. (7.35 moles) of epichlorohydrin. Because at the beginning of the addition of the epichlorohydrin only mild heat of reaction was noted, the reaction mixture was warmed to 60 C. At that point the reaction was sufiiciently vigorous that the temperature remained at 60-65 C. without external heating during addition of the remainder of the epichlorohydrin. The temperature was then allowed to increase to C. and it was maintained at 85-90 C. by moderate cooling for 0.75 hour. After standing overnight, a 6.0 g. sample of the reaction mixture was removed for analysis and to the remaining mixture of tris(2,3-dichloropropyl) phosphite and bis(2,3- dichloropropyl) phosphorochloridite there was added, during 0.3 hour, 83.5 g. (1.9 moles) of acetaldehyde while maintaining the temperature of the reaction mixture at 2030 C. by cooling. It was then warmed to reflux C.) and distilled to a pot temperature of C. and finally concentrated to C./2.0 mm. to give 987 g. of a colorless, liquid residue consisting of polyphosphonate-phosphites of the formulae:

1! (CHQQICHCICHzOMP O CIJHP (O CHzCHClCHzCl):

on, and

I II I l OCHPOCH-P(OCHzOHClQHgCl): ouzolonoionihln where n is 1.

A 300 g. sample of the polyphosphonate-phosphites CH3 OI CH: O

was placed in a 500 cc. flask and stirred and heated at 195-200 C. for 0.5 hour.

The reaction mixture was allowed to cool to 140 C. and then concentrated to C./0.5 mm. to give as residue 279.5 g. of phosphite-free polyphosphonates. Testing of the hydrolytic stability thereof by the procedure described in Example -4 gave a value of 0.548 milliequivalent of NaOH/ g. sample as compared to 1.302, the value obtained by like testing of the polyphosphonate-phosphite previous to the isomerization by heat.

Example 24 This example describes the preparation of phosphitefree polyphosphonate by the reaction of two moles of phosphorus tribromide with 4.9 moles of epichlorohydrin to give a mixture of phosphite and phosphorobromidite, reaction of the resulting mixture with acetaldehyde to obtain a polyphosphonatc-phosphite, and conversion of the latter to the phosphite-free product.

To a mixture consisting of 507.0 g. (1.87 moles) of phosphorus tribromide and 2.5 g. of ethylene chlorohydrin there was added 415 g. (4.49 moles) of epichlorohydrin during 0.3 hour. There was only mild heat of reaction, so the temperature was allowed to increase spontaneously during addition of the epichlorohydrin. The reaction mixture was then maintained at 5060 C. with mild cooling until there was no further heat of reaction (1.25 hour), and subsequently warmed for 0.5 hour at 5560 C. to assure complete reaction. After removing a 10.0 g. sample of the reaction mixture for analysis, the remaining mixture of tris(2-bromo-3-chloropropyl) phosphite and bis(2-bromo-3-chloropropyl) phosphorobromidite was cooled to 20 C. and there was added thereto 57 g. (1.29 moles) of acetaldehyde during 0.1 hour while maintaining the temperature at 20- 30 C. by cooling. When all of the aldehyde had been added, the mixture was kept at 50-55 C. for 0.5 hour by cooling and when there was no further evidence of exothermal reaction, an additional g. of acetaldehyde was added. A temperature rise of 1 C. was noted. The whole was then warmed to 80 C. and concentrated to 100 C./0.05 mm. to give by-product 2-bromo-1- chloropropane in the Dry Ice trap which formed part of the equipment and as residue 850 g. of polyphosphonate-phosphite product consisting of Found Caled. for

C15HHC1406P2 Percent O 35. 9 35. 68 Percent H 4. 42 4. 51 Percent 01 28. 3 28. 09 Percent P 12. 12. 04

Determination of the hydrolytic stability of this compound by the procedure of Example 4 gave a value of 2,590 milliequivalents of NaOl-I/ g. sample.

The presently prepared phosphite-phosphonate was converted to the phosphonate as follows: A 304 g. portion of the compound was transferred to a flask, heated at 198203 C./0.1 mm. for 0.5 hour and subsequently distilled to remove material boiling below 150 C./0.1 mm. There was thus obtained as residue 270.2 g. of a [bis(2 chloroethoxy)phosphinyl] benzyl 2 chloroethyl 2-chloroethylphosphonate of the formula CICHzCHz O Determination of the hydrolytic stability of this compound by the procedure of Example 4 gave a value of 0.876 milliequivalent of NaOH/ g. sample.

Example 26 Since it has been established that there is a close relationship between the quantity of a material required to suppress glowing and the eflectiveness of the same material for reducing preignition of a leaded fuel in gasoline engines, testing of the presently prepared polyphosphorus compounds was conducted by a glow test method wherein the following procedure was employed:

Test blends were prepared by blending (1) 5 ml. of a fuel consisting of a high-boiling (380-42'0" F.) hydro- 0 ll (CHgClCHBrCHzOhPOCHP(OCH CHBrCH Cl)1 and 7 r n at (CH;ClCHBrCH:O);P OCHP-OCHP(OCHgCHBrCHzCl):

l L CHzGlCHBrCHaO n where'n is 1.

Evaluation of the hydrolytic stability of the presently prepared polypliosphonatc-phosphite mixture using the method described in Example 4 gave a value of 0.304 milli'equivalent of NaOH/ g. sample.

A- 403 g. portion of the above mixture was stirred and heated r0200 CL, cooled to 150 C. and then concentrated to 190 C./0.3 mm. to give as residue 338 g. of the phosphite-free product. Testing of the hydrolytic stability of this product by the procedure of Example 4 gave a value of 0.115 milliequivalent of NaQH/ g. sample.

Example 25 To 1472 g. of a mixture consisting of 2.98 moles each of tris(2-chloroethyl) phosphite and bis(2-chloroethyl) phosphorochloridite there was added, during 0.5 hour, 318 g. (3.0 moles) of benzaldehyde with mild cooling to maintain the temperature of the reaction mixture at 1 527 C. The whole was then allowed to' Warm spontaneously to a maximum temperature of 43 C. and subsequently heat was applied and the reaction mixture was stirred at-70-95 C. for 2 hours. After standing overnight, the reaction mixture was then concentrated, with stirring, to a pot temperatureof 125 C./ 0.2 mm. to give as residue 1481 g. (99% theoretical yield) of the substantially pure bis(2-chloroethyl) phosphite' of bis(2- chloroethyl) a-hydroxybenzylphosphonate, n 1.5285, which analyzed as follows:

carbon fraction containing approximately mg. of lead based on the quantity of a commercial tetraethylleadhalohydrocarbon additive (hereinafter referred to as TEL) which had been incorporated therein and 1 ml. of an SAE 30 grade lubricating oil with (2) graduated, precisely weighed quantities of one of the polyphosphorus compounds to be tested, said quantities being in the range of 0:01 to 2.0 times the quantity of lead present. Two ml. of the test blend was then dropped at a constant rate (1.5i0.1 nil/l5 minutes), during a 15-17 minute period, onto a reagent grade decolorizing carbon contained in a crucible maintained in a furnace at a temperature which was high enough to keep the bottom of the crucible at ca. 1,000 P. By using test blends containing progressively lower quantities of the test compound, there was determined the minimum concentration of the test compound at which no glowing of the carbon was evidenced either during the dropping period or after all of the test sample had been added. Under these conditions, a control sample, i.e., one which contained all of the constituents of the test blend except the polyphosphorus compound caused the carbon to glow throughout addition thereof and after addition had been completed. On the other hand, no glowing was observed when there was present in the test blend 0.0400 g./5 m1. of said fuel of the polyphosphorus compound prepared by reacting two moles of phosphorus trichloride with 4.75 moles of propylene oxide to obtain a mixture of one molar equivalent of bis(2-chloropropy1) phosphoro- 

1. A PENTAVELENT PHOSPHRUS ESTER SELECTED FROM THE CLASS CONSISTING OF DIESTERS OF THE FORMULA:
 12. THE METHOD OF PREPARING A PENTAVALENT PHOSPHORUS DIESTER OF THE FORMULA 